Negative photosensitive resin composition, pattern structure and method for producing patterned cured film

Abstract

A new photosensitive resin composition based on a polysiloxane, that is, a negative photosensitive resin composition is provided. A negative photosensitive resin composition includes (A) a polysiloxane compound containing a first structural unit represented by the following general formula (1), (B) a photoinduced curing accelerator, and (C) a solvent.[(Rx)bR1mSiOn/2]  (1)

1 . A negative photosensitive resin composition comprising:
 (A) a polysiloxane compound containing a first structural unit represented by a following general formula (1);   (B) a photoinduced curing accelerator; and   (C) a solvent,
   [(R x ) b R 1   m SiO n/2 ]  (1)
 
   wherein, in the general formula (1), R x  is a monovalent group represented by a following general formula (1a),   
       
         
           
           
               
               
           
         
         R 1  is a substituent selected from a group consisting of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms and a fluoroalkyl group having 1 to 3 carbon atoms, 
         b is a number of 1 or more and 3 or less, m is a number of 0 or more and less than 3, n is a number of more than 0 and 3 or less, b+m+n=4, 
         when there are a plurality of R x  and R 1 , R x  and R 1  are independently selected from any of the substituents, and 
         in the general formula (1a), X is a hydrogen atom, a is a number of 1 or more and 5 or less, and a broken line represents a bond. 
       
     
     
         2 . The negative photosensitive resin composition according to  claim 1 , wherein the group represented by the general formula (1a) is any of the groups represented by following general formulas (1aa) to (1ad), 
       
         
           
           
               
               
           
         
         wherein in the general formulas (1aa) to (1ad), broken line represents a bond. 
       
     
     
         3 . The negative photosensitive resin composition according to  claim 1 , wherein the first structural unit is a single structural unit. 
     
     
         4 . The negative photosensitive resin composition according to  claim 1 , wherein the photoinduced curing accelerator is composed of a photoacid generator and/or a photobase generator. 
     
     
         5 . The negative photosensitive resin composition according to  claim 1 , wherein the solvent includes at least one compound selected from a group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate, γ-butyrolactone, diacetone alcohol, diglyme, methyl isobutyl ketone, 3-methoxybutyl acetate, 2-heptanone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, glycols and glycol ethers, and glycol ether esters. 
     
     
         6 . The negative photosensitive resin composition according to  claim 1  wherein the polysiloxane compound contains a second structural unit represented by a following general formula (2) and/or a third structural unit represented by a following general formula (3),
   [(R y ) c R 2   p SiO q/2 ]  (2)
 
   [(R W ) t SiO u/2 ]  (3)
 
 wherein in the general formula (2), R y  is a substituent selected from monovalent organic groups having 1 or more and 30 or less carbon atoms containing any of an epoxy group, an oxetane group, an acryloyl group, a methacryloyl group or a lactone group, 
 R 2  is a substituent selected from a group consisting of a hydrogen atom, an alkyl group having 1 or more and 3 or less carbon atoms, a phenyl group, a hydroxy group, alkoxy groups having 1 or more and 3 or less carbon atoms and fluoroalkyl groups having 1 or more and 3 or less carbon atoms, 
 c is a number of 1 or more and 3 or less, p is a number of 0 or more and less than 3, and q is more than 0 and 3 or less, and c+p+q=4, 
 when there are a plurality of R y  and R 2 , R y  and R 2  are independently selected from any of the substituents, 
 in the general formula (3), R W  is a substituent selected from a group consisting of a halogen group, an alkoxy group and a hydroxy group, and 
 t is a number of 0 or more and less than 4, u is a number of more than 0 and 4 or less, and t+u=4. 
 
     
     
         7 . The negative photosensitive resin composition according to  claim 6 , wherein the monovalent organic group R y  is a group represented by a following general formulas (2a), (2b), (2c), (3a), or (4a), 
       
         
           
           
               
               
           
         
         wherein in the general formula (2a), (2b), (2c), (3a), or (4a), R g , R h , R i , R j  and R k  each independently represent a divalent linking group, and a broken line represents a bond. 
       
     
     
         8 . The negative photosensitive resin composition according to  claim 6 , wherein the monovalent organic group R y  is a substituent selected from monovalent organic groups having 1 to 30 carbon atoms including any of an epoxy group, an acryloyl group, and a methacryloyl group. 
     
     
         9 . The negative photosensitive resin composition according to  claim 1 , wherein the polysiloxane compound has a weight average molecular weight of 500 to 50,000. 
     
     
         10 . The negative photosensitive resin composition according to  claim 1 , wherein in a weight average molecular weight (Mw 1 ) of the negative photosensitive resin composition and a weight average molecular weight (Mw 2 ) of a film obtained by applying the negative photosensitive resin composition to a substrate, exposing to light at 365 nm at 560 mJ/cm 2 , and curing by heating at 100° C. for 1 minute, a rate of increase in molecular weight represented by (Mw 2 -Mw 1 )/Mw 1  is 0.50 or more. 
     
     
         11 . A pattern structure comprising: a first structure formed on a substrate and containing (A) a polysiloxane compound containing a first structural unit represented by a following general formula (1A) and (B) a modified product of a photoinduced curing accelerator; and a second structure containing a component different from the first structure or a void
   [(R x1 ) b1 R 11   m1 SiO n1/2 ]  (1A)
   wherein in the general formula (1A), R x1  is a monovalent group represented by following general formula (1Aa),   
       
         
           
           
               
               
           
         
         R 11  is a substituent selected from a group consisting of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms and a fluoroalkyl group having 1 to 3 carbon atoms, 
         b1 is a number of 1 or more and 3 or less, ml is a number of 0 or more and less than 3, n1 is a number of more than 0 and 3 or less, b1+m1+n1=4, 
         when there are a plurality of R x1  and R 11 , R x1  and R 11  are independently selected from any of the substituent, and 
         in the general formula (1Aa), X1 is a hydrogen atom or a bond site with Si or C contained in a structural unit different from the first structural unit represented by the general formula (1A), al is a number of 1 or more and 5 or less, and a broken line represents a bond. 
       
     
     
         12 . The pattern structure according to  claim 11 , wherein the polysiloxane compound has a weight average molecular weight of 750 to 500,000. 
     
     
         13 . A method for producing a patterned cured film formed on a substrate comprising: applying a negative photosensitive resin composition including (A) a polysiloxane compound containing a first structural unit represented by a following general formula (1), (B) a photoinduced curing accelerator, and (C) a solvent to the substrate to form a photosensitive resin film,
 exposing the photosensitive resin film through a photomask, and   dissolving an unexposed portion of the photosensitive resin film with an alkaline solution
   [(Rx)bR1mSiOn/2]  (1)
 
   wherein in the general formula (1), R x  is a monovalent group represented by following general formula (1a),   R 1  is a substituent selected from a group consisting of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms and a fluoroalkyl group having 1 to 3 carbon atoms,   b is a number of 1 or more and 3 or less, m is a number of 0 or more and less than 3, n is a number of more than 0 and 3 or less, b+m+n=4,   when there are a plurality of R x  and R 1 , R x  and R 1  are independently selected from any of the substituent, and   in the general formula (1a), X is a hydrogen atom, a is a number of 1 or more and 5 or less, and a broken line represents a bond.   
     
     
         14 . The method for producing the patterned cured film according to  claim 13  further comprising: heating a patterned resin film obtained by dissolving the unexposed portion of the photosensitive resin film with the alkaline solution, thereby curing the patterned resin film to obtain the patterned cured film. 
     
     
         15 . The method for producing the patterned cured film according to  claim 13 , wherein the photosensitive resin film is exposed through the photomask by exposing to light having a wavelength of 1 nm to 600 nm. 
     
     
         16 . The method for producing the patterned cured film according to  claim 13  further comprising: the exposed photosensitive resin film is heated, after exposing the photosensitive resin film through the photomask, and dissolving the unexposed portion of the heated photosensitive resin film with the alkaline solution.